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Large structural effects in neutral and protonated species: a computational study
Author(s) -
Abboud JoséLuis M.,
Alkorta Ibon,
Dávalos Juan Z.
Publication year - 2001
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.448
Subject(s) - undecane , chemistry , ketone , protonation , diketone , isodesmic reaction , computational chemistry , hydrocarbon , stereochemistry , medicinal chemistry , organic chemistry , density functional theory , ion
The B3LYP/6‐31G(d) methodology was applied to the study of the diketone pentacyclo[5.4.0.0 2,6 .0 3,10 .0 5,9 ]undecane‐8,11‐dione ( 1 ), the hydrocarbon pentacyclo[5.4.0.0 2,6 .0 3,10 .0 5,9 ]undecane ( 2 ) and the ketone pentacyclo[5.4.0.0 2,6 .0 3,10 .0 5,9 ]undecane‐8‐one ( 3 ). Also examined were the oxygen‐protonated species 1 H + and 3 H + . The diketone pentacyclo[5.4.0.0 2,6 .0 3,10 .0 5,9 ]undecane‐4,8‐dione ( 4 ) and the ketone pentacyclo[5.4.0.0 2,6 .0 3,10 .0 5,9 ]undecane‐4‐one ( 5 ) and their protonated forms were used for comparison purposes. This information was used to construct several isodesmic reactions, allowing the quantitative estimate of the influence of the carbonyl groups on the stability of the various species in the gas phase. These results were in excellent agreement with the experimental thermochemical and structural data available. Analyses by means of the natural bond orbital theory and simple electrostatic models were also performed. Copyright © 2001 John Wiley & Sons, Ltd.